We achieve a considerable improvement in proposed schemes for the selective photoionization of odd mass zirconium isotopes. The technique implements intermediate-state alignment for isotope-selective laser excitation by broadband pulsed lasers, which incorporates the spectroscopic selection rules for the absorption of polarized light. The improvement includes newly found intermediate levels, where J = 0 character as a third excited-state intermediate, in cooperation with four-step photoexcitation (J = 2–1–1–0 scheme). Isotope selectivity (separation coefficient for 91Zr: >2400) has been identified in addition to a significant enhancement of ionization efficiency (30×) compared with previous research. A search for suitable third intermediate levels has covered over autoionizing Rydberg states in a singly ionized Zr II region (up to 58 000 cm−1). The measured autoionizing Rydberg states show high photoion yields but are not identified as favoured isotopic selectivity, as observed in the four-step photoionization. Prospects and future directions in laser even/odd-mass isotope separation are discussed.